MXPA02003764A - Phosphites. - Google Patents

Phosphites.

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Publication number
MXPA02003764A
MXPA02003764A MXPA02003764A MXPA02003764A MXPA02003764A MX PA02003764 A MXPA02003764 A MX PA02003764A MX PA02003764 A MXPA02003764 A MX PA02003764A MX PA02003764 A MXPA02003764 A MX PA02003764A MX PA02003764 A MXPA02003764 A MX PA02003764A
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aromatic
atom
joins
phosphorus atom
radical
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MXPA02003764A
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Spanish (es)
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Siegel Wolfgang
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Basf Ag
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/08—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds
    • C07C253/10—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds to compounds containing carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/141—Esters of phosphorous acids
    • C07F9/145—Esters of phosphorous acids with hydroxyaryl compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/52—Isomerisation reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Toxicology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
  • Steroid Compounds (AREA)

Abstract

The invention relates to phosphites of the formula (I) P (O R1)x (O R2)y (O R3)z (O R4)p where R1= an aromatic group with a C1 C18 alkyl substituent ortho to the O atom, or an aromatic substituent ortho to the O atom, or a fused aromatic system ortho to the O atom; R2= an aromatic group with a C1 C18 alkyl substituent meta to the O atom, or an aromatic substituent meta to the O atom, or a fused aromatic system meta to the O atom, whereby the aromatic residue ortho to the O atom has a hydrogen atom; R3 = an aromatic group with a C1 C18 alkyl substituent para to the O atom, or an aromatic substituent para to the O atom, whereby the aromatic group ortho to the O atom has a hydrogen atom; R4= an aromatic group with substituents ortho, meta and para to the o atom which are different to those defined for R1, R2 and R3, whereby the aromatic group ortho to the O atom has a hydrogen atom; x = 1 or 2; y, z and p, independent of each other = 0, 1 or 2 with the proviso, that xplus;yplus;zplus;p =3.

Description

PHOSPHITES.
Description The present invention relates to new phosphites, processes for their preparation, their use as ligands in transient metal complexes, new transient metal complexes, processes for their preparation, the use thereof as catalysts and processes in the presence of such complexes. transient metal as catalysts.
Triaryl phosphites, nickel complexes with such phosphites as ligands are known, as well as the use of such complexes as catalysts.
DE-OS 2 237 703, US-A-3, 850, 973 and US-A-3, 903, 120 describe a process for the hydrocyanuration of unsaturated organic compounds and the isomerization of nitriles in the presence of nickel complexes ( 0) with tri-o-tolyl phosphite as a ligand. The disadvantage in this procedure is that the stability of such nickel complexes is not satisfactory. This reduced stability is evidenced by a very low content of Ni (0), which is the active species for hydrocyanuration, in the reaction solution.
US-A-3,766,237 and US-A-3, 903, 120 describe a process for the hydrocyanuration of unsaturated organic compounds and the isomerization of nitriles in the presence of nickel (0) complexes with tri-m / p-tolyl -phosphite as a ligand. The disadvantage in this process is that the reactivity of such nickel complexes is unsatisfactory.
Therefore, the technical objective was to provide a procedure that would allow the hydrocyanuration of unsaturated organic compounds in a simple and economical manner, with a high stability and a high reactivity of the catalyst.
Therefore, phosphites of the formula I were found P (O-R1) (0-R2) and (0-R3) z (O-R4), P meaning R1: an aromatic radical with an alkyl substituent with 1 to 18 carbon atoms in the position or in front of the oxygen atom linking the phosphorus atom with the aromatic system, or an aromatic substituent in the position or in front of the oxygen atom joins the phosphorus atom with the aromatic system, or with an anellated system in position or in front of the oxygen atom that joins the phosphorus atom with the aromatic system, R2: an aromatic radical with an alkyl substituent with 1 to 18 carbon atoms in the m position opposite the oxygen atom, which joins the phosphorus atom with the aromatic system, or an aromatic substituent in the m position opposite the oxygen atom that joins the phosphorus atom with the aromatic system, or with an anellated system in the m position opposite the oxygen atom that joins the phosphorus atom with the aromatic system, carrying the aromatic radical in position or in front of the oxygen atom that joins the phosphorus atom with the aromatic system, a hydrogen atom, R3: an aromatic radical with an alkyl substituent with 1 to 18 carbon atoms in the p-position against the oxygen atom linking the phosphorus atom with the aromatic system, or with an aromatic substituent in the p-position against the oxygen atom that joins the phosphorus atom with the aromatic system, carrying the aromatic radical in position or in front of the oxygen atom that joins the phosphorus atom with the aromatic system, a hydrogen atom, R: an aromatic radical, which carries in the positions o, m and p in front of the oxygen atom joining the phosphorus atom with the aromatic system, other substituents than those defined for R1, R2 and R3, carrying the aromatic radical in the position or in front of the oxygen atom that joins the phosphorus atom with the aromatic system, a hydrogen atom, x: 1 or 2, y, z, p: independently, 0, 1 or 2, being precise that x + y + z + p = 3, as well as methods for obtaining them, the use thereof as ligands in transient metal complexes, new transient metal complexes, processes for obtaining them, the use thereof as catalysts and processes in the presence of such transient metal complexes as catalysts. .
According to the invention, the radical R 1 means an aromatic radical having 1 to 18 carbon atoms in the position or in front of the oxygen atom linking the phosphorus atom with the aromatic system, or .íí.jftití-É.iiiÉli "* ---" --- •• -----.- »----» ..-- an aromatic substituent in the position or in front of the oxygen atom that binds the phosphorus atom with the aromatic system, or an annealing system in position or in front of the oxygen atom that joins the phosphorus atom with the aromatic system.
As the aromatic radical, the heterocycle, preferably hom- nolene, and the phenyl radical are suitable.
The aromatic radical can carry other functional groups, such as alkoxy or halogen groups, for example, chlorine or bromine; Preferably, the aromatic radical carries no substituents.
The aromatic radical carries, according to the invention, an alkyl substituent with 1 to 18 carbon atoms in the position or at the 15 oxygen atom that joins the phosphorus atom with the aromatic system, or an anellated system in the position or in front of the oxygen atom that joins the phosphorus atom with the aromatic system. As the alkyl radical, linear or cyclic radicals having 1 to 18 carbon atoms, preferably radicals, are suitable 20 with 1 to 9 carbon atoms, such as, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, n-pentyl radicals, as well as their isomers, radicals n hexyl, as well as their isomers, cyclopentyl or cyclohexyl radicals, the cyclic alkyl radicals being able to carry linear alkyl radicals or other cyclic alkyl radicals or aromatic radicals and the alkyl radicals being able to carry cyclic alkyl radicals or aromatic radicals as substituents. Preferred alkyl radicals are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl. These alkyl radicals can carry other functional groups, such as, for example, alkoxy groups, amino groups, such as, for example, unsubstituted, monosubstituted or disubstituted amino groups, mercapto groups, such as, for example, substituted mercapto groups, it being possible to carry out the substitution by the aforementioned alkyl groups or the mentioned aromatic radicals. Preferably, the alkyl radicals will not carry any functional groups.
In the alkyl radicals the carbon atoms may be substituted by other atoms, such as, for example, oxygen, nitrogen or sulfur; preferably the alkyl radicals will not be substituted.
Four. Five As the aromatic substituent, the heterocycle, preferably hom- ylene, such as, for example, the phenyl radical, is suitable.
The aromatic substituent can carry other functional groups, such as, for example, alkoxy or halogen groups, for example chlorine or bromine; preferably, the aromatic substituent will not carry any functional groups.
The aromatic substituent may carry one or more alkyl substituents with 1 to 18 carbon atoms or one or more aromatic anellated systems, or carry no other substituents.
Suitable alkyl radicals are radicals having 1 to 18 linear or cyclic carbon atoms, preferably radicals having 9 carbon atoms, such as, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i- butyl, s-butyl, n-pentyl radicals, as well as, for example, their isomers, n-hexyl radicals, as well as, for example, their isomers, cyclopentyl or cyclohexyl radicals, cyclic alkyl radicals being able to carry linear alkyl radicals or other cyclic alkyl radicals or aromatic radicals and the alkyl radicals being able to carry cyclic alkyl radicals or aromatic radicals as substituents. Preferred alkyl radicals are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl groups.
These alkyl radicals can carry other functional groups, such as, for example, alkoxy groups, amino groups, such as, for example, unsubstituted, mono- or di-substituted amino groups, mercapto groups, such as, for example, substituted mercapto groups, the substitution being possible. by the aforementioned alkyl groups or the aromatic radicals mentioned. Preferably, the alkyl radicals will not carry any functional groups.
In the alkyl radicals, the carbon atoms may be substituted by other atoms, such as, for example, oxygen, nitrogen or sulfur; preferably the alkyl radicals will not be substituted.
As radical R1, o-tolyl, o-ethyl-phenyl, on-propyl-phenyl, o-isopropyl-phenyl, on-butyl-phenyl, o-sec-butyl-phenyl, o-tert-butyl-phenyl, are advantageous. groups (o-phenyl) -phenyl or 1-naphthyl.
According to the invention, the radical R2 is an aromatic radical with an alkyl substituent with 1 to 18 carbon atoms in the m-position opposite the oxygen atom linking the phosphorus atom with the aromatic system, or with an aromatic substituent in the m-position in front of the oxygen atom that joins the phosphorus atom with the aromatic system, or with an anellated system in the m position in front of the oxygen atom that joins the phosphorus atom with the aromatic system, carrying the aromatic radical in the position or front to the oxygen atom that joins the phosphorus atom with the aromatic system, a hydrogen atom.
As the aromatic radical, the heterocycle, preferably hom- ylene, such as, for example, the phenyl radical, is suitable.
The aromatic radical can carry other functional groups, such as, for example, alkoxy or halogen groups, for example chlorine or bromine; preferably, the aromatic radical will not carry any functional groups.
According to the invention, the aromatic radical carries an alkyl substituent with 1 to 18 carbon atoms in the m position opposite the oxygen atom joining the phosphorus atom with the aromatic system, or a system attached at the m position to the atom of oxygen that joins the phosphorus atom with the aromatic system. Suitable alkyl radicals are linear or cyclic radicals having 1 to 18 carbon atoms, preferably radicals having 1 to 9 carbon atoms, such as, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, butyl, s-butyl, n-pentyl radicals, as well as, for example, their isomers, n-hexyl radicals, as well as, for example, their isomers, cyclopentyl or cyclohexyl radicals, cyclic alkyl radicals being able to carry linear alkyl radicals or other cyclic alkyl radicals or aromatic radicals and the alkyl radicals being able to carry cyclic alkyl radicals or aromatic radicals as substituents. Preferred alkyl radicals are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl groups.
These alkyl radicals can carry other functional groups, such as, for example, alkoxy groups, amino groups, such as, for example, unsubstituted, mono- or di-substituted amino groups, mercapto groups, such as, for example, substituted mercapto groups, which can be substituted by the aforementioned alkyl groups or the aromatic radicals mentioned. Preferably, the alkyl radicals will not carry any functional groups.
In the alkyl radicals, the carbon atoms may be substituted by other atoms, such as, for example, oxygen, nitrogen or sulfur; preferably the alkyl radicals will not be substituted.
As the aromatic substituent, the heterocycle, preferably hom- ylene, such as, for example, the phenyl radical, is suitable.
The aromatic substituent can carry other functional groups, such as, for example, alkoxy or halogen groups, for example chlorine or bromine; preferably, the aromatic substituent will not carry any functional groups.
The aromatic substituent can carry one or more alkyl substituents with 1 to 18 carbon atoms or one or more aromatic systems which are anellated or do not carry any other substituents.
Suitable alkyl radicals are linear or cyclic radicals having 1 to 18 carbon atoms, preferably radicals having 1 to 9 carbon atoms, such as, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, n-pentyl radicals, as well as, for example, their isomers, n-hexyl radicals, as well as, for example, their isomers, cyclopentyl or cyclohexyl radicals, cyclic alkyl radicals being able to carry linear alkyl radicals or other cyclic alkyl radicals or aromatic radicals, and the alkyl radicals being able to carry cyclic alkyl radicals or aromatic radicals as substituents. Preferred alkyl radicals are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl groups.
These alkyl radicals can carry other functional groups, such as, for example, alkoxy groups, amino groups, such as, for example, unsubstituted, mono- or di-substituted amino groups, mercapto groups, such as, for example, substituted mercapto groups, which can be substituted by the aforementioned alkyl groups or the aromatic radicals mentioned. Preferably, the alkyl radicals will not carry any functional groups.
In the alkyl radicals the carbon atoms may be substituted by other atoms, such as, for example, oxygen, nitrogen or sulfur, substitute sein; preferably the alkyl radicals will not be substituted.
As radical R2, m-tolyl, m-ethyl-phenyl, mn-propyl-phenyl, m-isopropyl-phenyl, mn-butyl-phenyl, m-sec-butyl-phenyl, m-tert-butyl-phenyl are advantageous. (m-phenyl) -phenyl- or 2-naphthyl groups.
According to the invention, the radical R3 is an aromatic radical with an alkyl substituent with 1 to 18 carbon atoms in the p position opposite the oxygen atom linking the phosphorus atom with the aromatic system, or with an aromatic substituent in the position lii ^ jj ^ ¿^ p versus the oxygen atom that joins the phosphorus atom with the aromatic system, carrying the aromatic radical in position or in front of the oxygen atom that joins the phosphorus atom with the aromatic system, an atom of hydrogen.
As the aromatic radical, the heterocycle, preferably hom- ylene, such as, for example, the phenyl radical, is suitable.
The aromatic radical can carry other functional groups, such as, for example, alkoxy or halogen groups, for example chlorine or bromine; preferably, the aromatic radical will not carry any functional groups.
According to the invention, the aromatic radical has an alkyl substituent with 1 to 18 carbon atoms in the p-position opposite the oxygen atom linking the phosphorus atom with the aromatic system or an aromatic system attached in the p-position to the atom of oxygen that joins the phosphorus atom with the aromatic system. Suitable alkyl radicals are linear or cyclic radicals having 1 to 18 carbon atoms, preferably radicals having 1 to 9 carbon atoms, such as, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, n-pentyl radicals, as well as, for example, their isomers, n-hexyl radicals, as well as, for example, their isomers, cyclopentyl or cyclohexyl radicals, cyclic alkyl radicals being able to carry linear alkyl radicals or other cyclic alkyl radicals or aromatic radicals and the alkyl radicals being able to carry cyclic alkyl radicals or aromatic radicals as substituents. Preferred alkyl radicals are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl groups.
These alkyl radicals can carry other functional groups, such as, for example, alkoxy groups, amino groups, such as, for example, unsubstituted, mono- or di-substituted amino groups, mercapto groups, such as, for example, substituted mercapto groups, which can be substituted by the aforementioned alkyl groups or the aromatic radicals mentioned. Preferably, the alkyl radicals will not carry any functional groups.
In the alkyl radicals, the carbon atoms may be substituted by other atoms, such as, for example, oxygen, nitrogen or sulfur; preferably the alkyl radicals will not be substituted.
As the aromatic substituent, the heterocycle, preferably hom- ylene, such as, for example, the phenyl radical, is suitable.
The aromatic substituent can carry other functional groups, such as, for example, alkoxy or halogen groups, for example chlorine or bromine; preferably, the aromatic substituent will not carry any functional groups.
The aromatic substituent can carry one or more alkyl substituents with 1 to 18 carbon atoms or one or more aromatic systems which are anellated or do not carry any other substituents.
Suitable alkyl radicals are linear or cyclic alkyl radicals having 1 to 18 carbon atoms, preferably radicals having 1 to 9 carbon atoms, as eg. methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, n-pentyl radicals, as well as e.g. its isomers, n-hexyl radicals, as well as, for example, its isomers, cyclopentyl or cyclohexyl radicals, the cyclic alkyl radicals being able to carry linear alkyl radicals or other cyclic alkyl radicals or aromatic radicals and the alkyl radicals being able to carry cyclic or radical alkyl radicals aromatics as substituents. Preferred alkyl radicals are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl groups.
These alkyl radicals can carry other functional groups, such as, for example, alkoxy groups, amino groups, such as, for example, unsubstituted, mono- or di-substituted amino groups, mercapto groups, such as, for example, substituted mercapto groups, which can be substituted by the aforementioned alkyl groups or the aromatic radicals mentioned. Preferably, the alkyl radicals will not carry any functional groups.
In the alkyl radicals, the carbon atoms may be substituted by other atoms, such as, for example, oxygen, nitrogen or sulfur; preferably the alkyl radicals will not be substituted.
As radical R3, p-tolyl, p-ethyl-phenyl, pn-propyl-phenyl, p-isopropyl-phenyl, p-butyl-phenyl, p-sec-butyl-phenyl, p-tert-butyl-phenyl groups are advantageous. or groups (p-phenyl) -phenyl.
According to the invention, the radical R 4 is an aromatic radical which at the positions o, m and p to the oxygen atom linking the phosphorus atom with the aromatic system, carries other substituents than those defined for R 1, R 2 and R 3, with the radical aromatic in the position or in front of the oxygen atom that joins the phosphorus atom with the aromatic system, a hydrogen atom.
The aromatic radical can carry functional groups, such as, for example, alkoxy or halogen groups, for example chlorine or bromine; preferably, the aromatic radical will not carry any functional groups.
As radical R4, the phenyl radical is preferably appropriate.
Of the radicals R.sub.1, R.sub.2, R.sub.3 or R.sub.4, two or three in the formula I can be linked together via alkylene groups having 1 to 18 carbon atoms or directly.
Suitable alkylene groups are linear or cyclic radicals having 1 to 18 carbon atoms, preferably radicals having 1 to 9 carbon atoms, such as, for example, methylene, ethylene, n-propylene, n-butylene radicals, n- pentylene, as well as, for example, its isomers, n-hexyl radicals, as well as, for example, its isomers, cyclopentyl or cyclohexyl radicals, the cyclic alkyl radicals being able to carry linear alkyl radicals or other cyclic alkyl radicals or aromatic radicals and the alkyl radicals carry cyclic alkyl radicals or aromatic radicals as substituents, as for example, in the radicals 1-methylethylene, 1, 1-dimethylethylene, 1, 2-dimethylethylene, 1-methyl-n-propylene, 2-methyl -n-propylene, 1,1-dimethyl-n-propylene, 1,2-dimethyl-n-propylene, 1,3-dimethyl-n-propylene, 2,2-dimethyl-n-propylene.
The alkylene radicals can also carry other functional groups, such as, for example, alkoxy groups, amino groups, such as, for example, unsubstituted, mono- or di-substituted amino groups, mercapto groups, such as, for example, substituted mercapto groups, the substitution being possible. by the alkyl groups mentioned in the definition of the radicals R1, R2 or R3 or by the mentioned aromatic radicals. Preferably, the alkyl radicals will not carry any functional groups.
In the alkylene radicals the carbon atoms may be substituted by other atoms, such as, for example, oxygen, nitrogen or sulfur; preferably, the alkylene radicals will not be substituted.
According to the invention, the index x is 1 or 2.
According to the invention, the indices y, z y mean, independently, 0, 1 or 2, it being necessary that the sum of the indices x, y, z and p, namely, x + y + z + p, amount to 3.
Preferably, p is equal to 0.
Hence, according to the invention, the following possibilities for the indices x, y, z and p result: Particularly preferred phosphites are those, in which R 1 represents the o-isopropyl-phenyl radical, R 2 represents the m-tolyl radical and R 3 is the p-tolyl radical with the indices mentioned in the table, those, in which R 1 represents the o-tolyl radical, R2 means the m-tolyl radical and R3 is the p-tolyl radical with the indices mentioned in rabies, those in which R1 represents the 1-naphthyl radical, R2 means the radical m-tolyl and R3 is the p-tolyl radical with the indices mentioned in the table, those in which R 1 signifies the o-tolyl radical, R 2 signifies the 2-naphthyl radical and R 3 is the p-tolyl radical with the indices mentioned in the felling, those , wherein R 1 is the o-isopropyl radical, R 2 is the 2-naphthyl radical and R 3 is the p-tolyl radical with the abovementioned indexes, as well as mixtures of these phosphites.
The phosphites of the formula I are obtained a) reacting a phosphoric trihalide with an alcohol selected from the group encompassing R ^ H, R2OH, R3OH and R4OH or their mixtures, obtaining a monoester of dihalogenophosphorous acid, transforming the aforementioned dihalogenophosphorous acid monoester with an alcohol selected from the group comprising ROH, R20H, R30H and R40H or mixtures thereof, obtaining a diester of monohalophosphonous acid, and c) by reacting the aforementioned monohalophosphonous acid diester with an alcohol selected from the group comprising R ^ H, R20H, R30H and R4OH or mixtures thereof, obtaining a phosphite of the formula I.
The reaction can be carried out in three subsequent stages.
Two or three stages can be combined, namely, a with b or b with c.
All stages a, b and c can be combined with each other.
Suitable parameters and suitable amounts of the alcohols selected from the group comprising R ^ H, R2OH, R3OH and R4OH or their mixtures can be easily determined by some simple preliminary tests.
As the phosphoric trihalides, basically all phosphoric trihalides, preferably those in which Cl, Br, I, especially Cl, as well as their mixtures are used as the halide. It is also possible to use mixtures of different phosphines substituted by an identical or different halogen such as phosphoric trihalide. PC13 is especially preferred.
In steps a, b and c the reaction can advantageously be carried out at temperatures in the region of 10 to 200 ° C, preferably 50 to 150 ° C, especially 70 to 120 ° C.
In steps a, b and c, a molar ratio between the halide radicals and hydroxyl groups used in the different steps in the region of 1: 10 to 10: 1, preferably 1: 3 to 3: 1, is preferably applied.
The reaction in steps a, b and c can be carried out in the presence of an inorganic or organic diluent, especially a liquid diluent, such as, for example, an ester, for example ethyl acetate, an ether, for example, methyl t -butyl ether, diethyl ether, dioxane, tetrahydrofuran, an aromatic compound, for example, toluorene, or a halogenated hydrocarbon, for example, a halogenated hydrocarbon, such as tetrachloromethane, chloroform, methylene chloride, or a mixture of diluents of this type.
Preferably, the reaction is carried out without an inorganic or organic diluent of this type.
The generated hydrogen halide which is usually obtained in gaseous form under the reaction conditions can advantageously be separated and introduced into known chemical processes.
Generally, mixtures containing the desired component are obtained in steps a, b and c.
The desired component can be separated in a manner known per se, for example by extraction or distillation, preferably by distillation.
If the separation is effected by distillation, then it has proven advantageous to reduce the pressure to a value below the ambient pressure.
The distillation is advantageously carried out in a column, for example, with lateral outlet, or in several columns, for example in two, three or four columns.
Columns that are known per se are suitable as columns, such as columns with bell plates, columns with perforated plates or filling columns.
The optimal process conditions for the separation of the phosphite corre spondents of the formula I can easily be determined in each case by means of some simple preliminary tests.
The phosphites of the formula I can be used as ligands in transient metal complexes.
As transient metals, the metals of the first, second and sixth to eighth secondary group of the periodic system of elements are advantageous, those of the eighth secondary group of the periodic system, especially iron, cobalt and nickel, especially nickel, are especially preferred.
When nickel is used, it can be present in different valences, such as 0, +1, +2, +3. Nickel (0) and nickel (+2), especially nickel (0), are preferred here.
To obtain the transient metal complexes, a chemical compound containing a transient metal or, preferably, a transient metal can be transformed with a phosphite of the formula I um, it being possible to use it as a phosphite of the individual formula I or a mixture of several phosphites of the formula I.
The transient metal can be obtained prior to the reaction from suitable chemical compounds, for example by reduction with non-noble metals, eg zinc, from salts, such as, for example, chlorides.
If a compound containing a transition metal is used to obtain the transient metal complexes, salts, such as, for example, chlorides, bromides, acetylacetonates, sulphides, nitrates, for example, nickel chloride (2), are advantageously suitable.
After the reaction of the compound containing a transient metal or the transient metal with a phosphite of the formula I, the valence of the transient metal in the complex can be modified with suitable oxidants or reducing agents, for example common metals, such as, for example, zinc or hydrogen in a chemically bound form, such as, for example, sodium boron hydride or in a molecular or electrochemically modified form.
The molar ratio between the transient metal and the phosphite of the formula I in the transient metal complexes may vary from 1 to 6, preferably 2 to 5, especially 2, 3 or 4.
Transient metal complexes may be free of other ligands than the phosphites of formula I.
The transient metal complexes may contain, together with the phosphites of the formula I, other ligands, for example nitriles, such as, for example, acetonitrile, adiponitrile, 3-pentenenitrile, 4-pentenenitrile, 2-methyl-3-butenonitrile, Olefins, such as, for example, butadiene.
Transient metal complexes can be obtained, basically, as described in the literature, for example, in DE-OS-2 237 703, US-A-3, 850, 973, US-A-3, 766, 237 or US-A-3,903,120, for obtaining transient metal complexes, which contain tri-o-tolyl-phosphite, tri-m-tolyl-phosphite or tri-p-tolyl-phosphite, replacing these phosphites partially or completely by the phosphites of the formula I according to the invention.
Transient metal complexes can be used as catalysts, especially, as homogeneous catalysts.
It has proven especially advantageous to use the transient metal complexes of the invention as catalysts in the addition of hydrocyanic acid to olefinic double bonds, especially those in conjugation against other olefinic double bonds, for example, of butadiene, obtaining a mixture which contains 2-methyl-3-butenonitrile and 3-pentennitrile. It is also advantageous to use them as catalysts in the addition of hydrocyanic acid to olefinic double bonds, which are not conjugated with other olefinic double bonds, for example of 3-pentenenitrile or 4-pentenenitrile or their mixtures, preferably 3-pentenenitrile, obtaining adiponitrile, or 3-pentenoic acid ester or 4-pentenoic acid ester or mixtures thereof, preferably 3-pentenoic acid ester, obtaining 5-cianovaleric acid ester.
It has also proved advantageous to use the transient metal complexes of the invention as catalysts in the isomerization of organic nitriles, especially those, in which the mithril group is not conjugated with an olefinic double bond, for example, of 2-methyl. 3-butenonitrile, 3-pentenenitrile being obtained. It is also advantageous to use them as catalysts in the isomerization of organic nitriles, in which the nitrile group is conjugated with an olefinic double bond.
Procedures for addition of hydrocyanic acid to an olefinic double bond or isomerization of organic nitriles can be performed, in principle, as described in the literature for the use of transient metal complexes containing tri-o-tolyl-phosphite, tri -m-tolyl-phosphite or tri-p-tolyl-phosphite, these phosphites being partially or completely substituted by phosphites of the formula I according to the invention.
In these processes the transient metal complexes of the invention exhibit higher stability, as compared to those, which contain tri-o-tolyl phosphite as a ligand, and a higher reactivity as compared to those, which contain tri-m / p-tolyl-phosphite as a ligand.
Examples Example 1 A solution from CIP (O-m-tol) 2 (298 g, 1.06 mol) in n-hexane (2.5 1) is cooled to 0 ° C (ice bath). Two triethylamine (118 g, 1.17 mol) and o-cresol (114.5 g, 1.06 mol) are introduced through parallel funnels in parallel, within 2 h at 0 - 5 ° C. The reaction mixture is stirred for 12 h at room temperature. The precipitated NEt3'HCl is filtered with a vacuum filter under pressure and washed with n-hexane (250 ml). This preparation is repeated in a similar volume (1015 moles). Both crude solutions are collected and filtered through a column filled with A1203 to remove the remaining amounts of chlorine. After concentration in the rotary evaporator (16 mbar, 50 ° C), P (O-m-tol) 2 (O-o-tol) (Ll) is obtained as a yellow oil; Yield 695 g (1.97 moles, 95%). GC 95.6%. Anal. cale, for C21H2103P: C, 71.61; H, 5.96; P, 8.79. Gef: C, 71.6; H, 6.0; P, 8.8. ? NMR (CDCl3) d7.20-6.85 (m, 12), 2.24 (s, 6, C6H4-m-CH3), 2.21 (s, 3, C6H4 -? - CH3). 13C NMR (CDCl3) dl51.6, 150.2, 139.7, 131.3, 129.7, 129.3, 126.8, 124.9, 124.1, 121.4, 120.2, 117.7, 21.2, 16. 7. 31P NMR (CDCl3) dl29.7.
Examples 2 - 9 Ligands L2-L9 were prepared in analogy to Ll, the results are shown in Table 1.
Table 1: Examples 2 - 9 Ex emplos 10 - 12 A mixture of m-cresol, p-cresol and o-isopropylphenol with the molar composition indicated in Table 2 (total, 18 moles) is introduced as initial charge in a four-necked flask of 41. The mixture is heated under inert gas at 70 ° C. Within 5 h PC13 drops (824 g, 6 moles) are added. The HCl formed is removed via a washing tower. The temperature is increased to 110 ° C. While stirring slightly a stream of nitrogen is passed through the reaction mixture, until the development of HCl is complete.
Table 2: Examples 10 - 12 Example 13 Ligand Ll of Example 1 (378.3 g, 3-pentenenitrile (99.6 g), nickel powder (29.8 g) and CIP (Om-tol) 2 (1.51 g) are stirred under inert gas for 25 h at 95 ° C. After cooling to room temperature the excess nickel powder is filtered The filtrate contains 1.65% by weight of Ni (0) .The filtrate is diluted with 3-pennenitrile and additional ligand to a ligand: nickel (O) ratio of 18: 1 and a nickel (O) concentration of 0.8% by weight (Ni (0).) This solution is used as the catalyst solution (Kl) in Example 19.
Example 14 The ligand L2 of Example 2 (135.5 g), 3-pentenenitrile (36 g), nickel powder (10 g), CIP (Om-tol) 2 (0.5 g) and PC13 (6 drops) are stirred under inert gas for 24 h at 95 ° C. After cooling to room temperature the excess nickel powder is filtered. The filtrate contains 1.55% by weight of Ni (0). The filtrate is diluted with 3-pentenenitrile and additional ligand at a ligand: nickel (O) ratio of 18: 1 and a nickel (O) concentration of 0.7% by weight of Ni (O). This solution is used as the catalytic solution (K2) in Example 20.
Example 15 Ligand L3 of Example 3 (358.4 g), 3-pentenenitrile (94.4 g), nickel powder (28.2 g) and CIP (O-m-tol) 2 (1.43 g) are stirred under inert gas for 25 h at 95 ° C. After cooling to room temperature the excess nickel powder is filtered. The filtrate contains 1.28% e weight of Ni (0). The filtrate is diluted with 3-pentenenitrile and additional ligand to a ligand: nickel (O) ratio of 18: 1 and a concentration of (O) of 0.7% by weight of Ni (O). This solution is used as the catalytic solution (K3) in Example 21.
Example 16 The ligand IOL of Example 10 (780 g), 3-pentenenitrile (206 g), nickel powder (60 g), CIP (Om-tol) 2 (3.3 g) and PCl 3 (35 drops) are stirred under inert gas for 21 h at 95 ° C. After cooling to room temperature the excess nickel powder is filtered. The filtrate contains 1.5% by weight of Ni (0). The filtrate is diluted with 3-pentenenitrile and additional ligand at a ligand: nickel (O) ratio of 18: 1 and a nickel (O) concentration of 0.7% by weight of (Ni (O).) This solution is used as catalytic solution (K4) in Example 22.
Example 17 The ligand Lll of Example 11 (780 g), 3-pentenenitrile (206 g), nickel powder (60 g), CIP (Om-tol) 2 (3.3 g) and PC13 (35 drops) are stirred under gas inert for 29 h at 95 ° C. After cooling to room temperature the excess nickel powder is filtered. The filtrate contains 1.1% by weight of Ni (O). The filtrate is diluted with 3-pentenenitrile and additional ligand at a ligand: nickel (O) ratio of 18: 1 and a nickel (O) concentration of 0.7% by weight of (Ni (O).) This solution is used as catalytic solution (K5) in Example 23.
Example 18 The ligand L12 of Example 12 (500 g), 3-pentenenitrile (132 g), nickel powder (40 g), CIP (Om-tol) 2 (2.1 g) and PC13 (23 drops) are stirred under inert gas for 23 h at 95 ° C. One sample contains 0.72% by weight of Ni (O). Add another 20 g of nickel powder, as well as 1 g of CIP (O-m-tol) 2, and stir again for 18 h at 95 ° C. After cooling to room temperature the excess nickel powder is filtered. The filtrate contains 0.77% by weight of Ni (O). The filtrate is diluted with 3-pentenenitrile and additional ligand at a ligand: nickel (O) ratio of 18: 1 and a nickel (O) concentration of 0.6% by weight of Ni (0). This solution is used as the catalytic solution (K6) in Example 24.
Examples 19 - 26 Each time 50 mmoles of 2-methyl-3-butenonitrile (2M3BN) are reacted with the catalyst solution Kl-6 of Examples 13 -18 (0.2 mmole of Ni) for 2 h at 130 ° C. To exclude decomposition processes by air or humidity, the reactions are carried out in a closed system. At the end of the reaction, the conversion and selectivity by GC are determined. For comparison purposes, a solution of Ni complex (m- / p-tolylphosphite (m / p-tolylphosphite: Ni =) is used under identical conditions (50 mmoles of 2M3BN, 0.2 mmoles of Ni, 130 ° C, 2 h). 18: 1, 0.7% by weight of Ni (O), obtaining the complex solution analogous to that for Kl-6 from m / p-tolylphosphite and nickel powder in the presence of 3-pentenenitrile (Example 25).
Table 3: Examples 19 - 26

Claims (1)

1. A process for preparing transition metal complexes which comprises reacting Ni (O) or a chemical compound containing Ni (0) with a phosphite of the formula I P (0-R1), (0-R2) and (0-R3) 2 (0-R) p I meaning R1: an aromatic radical with an alkyl substituent with 1 to 18 carbon atoms in the position or in front of the oxygen atom that joins the phosphorus atom with the aromatic system, or having an aromatic substituent in the position or in front of the oxygen atom that joins the phosphorus atom with the aromatic system, or having an aromatic system condensed in the position or in front of the oxygen atom that joins the phosphorus atom with the aromatic system, R2: an aromatic radical with an alkyl substituent with 1 to 18 carbon atoms in the m position opposite the oxygen atom, which joins the phosphorus atom with the aromatic system, or having an aromatic substituent in the m position opposite the atom of oxygen that binds the phosphorus atom with the aromatic system, or having an aromatic system condensed in the m position opposite the oxygen atom that joins the phosphorus atom with the aromatic system, where the aromatic radical carries a hydrogen atom in the position or in front of the oxygen atom that joins the phosphorus atom with the aromatic system. R3: an aromatic radical with an alkyl substituent with 1 to 18 carbon atoms in the p-position against the oxygen atom linking the phosphorus atom with the aromatic system, or having an aromatic substituent in the p-position against the oxygen atom that joins the phosphorus atom with the aromatic system, where the aromatic radical carries a hydrogen atom in the position or in front of the oxygen atom that joins the phosphorus atom with the aromatic system. R4: an aromatic radical, which carries other substituents than those defined for R1, R2 and R3 at the positions o, m and p to the oxygen atom linking the phosphorus atom with the aromatic system, where the aromatic radical carries one atom of hydrogen in the position or in front of the oxygen atom that joins the phosphorus atom with the aromatic system. x: 1 or 2, and, z, p: independently of one another, 0, 1 or 2, with the proviso that x + y + z + p = 3. A process according to claim 1, using a phosphite of the formula I in which p = 0. A process according to claim 1 or 2, using a phosphite of the formula I, wherein the radicals R 1, R 2, R 3 and R 4 are selected, independently of one another, from the group comprising the naphthyl radical, the phenyl radical not substituted and the substituted phenyl radicals according to claim 1. A process according to any of clauses 1 to 3, using a phosphite of the formula I, wherein the radicals R1, R2, R3 and R4 are substituted or unsubstituted phenyl radicals. A transition metal complex obtainable according to any one of claims 1 to 4. The use of transition metal complexes according to claim 5 as a catalyst. The use according to claim 6 as a catalyst for the addition of hydrocyanic acid to an olefinic double bond. The use according to claim 6 as a catalyst for the isomerization of organic nitriles. A process for the addition of hydrocyanic acid to an olefinic double bond in the presence of a transition metal complex according to claim 5 as a catalyst. A process according to claim 9, wherein hydrocyanic acid is added to butadiene, obtaining a compound selected from the group consisting of 2-methyl-3-buten-nitrile and 3-pentene-nitrile. A process for the isomerization of organic nitriles in the presence of a transition metal complex according to claim 5 as a catalyst. A process according to claim 11, wherein 2-methyl-3-buten-nitrile is isomerized to 3-pentene-nitrile. SUMMARY OF THE INVENTION. Phosphites of the formula I P (O-R1), (0-R2) and (0-R3) 2 (0-R) p I meaning R1: an aromatic radical with an alkyl substituent with 1 to 18 10 carbon atoms in the position or in front of the oxygen atom that joins the phosphorus atom with the aromatic system, or an aromatic substituent in the position or in front of the oxygen atom that joins the phosphorus atom with the aromatic system, or with an anellated system in the position or in front of the oxygen atom that joins the phosphorus atom with the aromatic system, R2: an aromatic radical with an alkyl substituent with 1 to 18 carbon atoms in the m position opposite the oxygen atom, which joins the phosphorus atom with the aromatic system, or an aromatic substituent in the m position opposite the atom of oxygen that joins the phosphorus atom with the aromatic system, or with an anellated system in the m position in front of the oxygen atom that joins the phosphorus atom with the aromatic system, carrying the aromatic radical in the position or in front of the atom of oxygen that binds the phosphorus atom with the aromatic system, a hydrogen atom, R: an aromatic radical with an alkyl substituent with 1 to 18 carbon atoms in the p-position against the oxygen atom 30 that joins the phosphorus atom with the aromatic system, or with an aromatic substituent in the p position opposite the oxygen atom that joins the phosphorus atom with the aromatic system, carrying the aromatic radical in position or in front of the oxygen atom that binds the phosphorus atom with the system 35 aromatic, a hydrogen atom, R1: an aromatic radical, which carries in the positions o, m and p opposite the oxygen atom joining the phosphorus atom with the aromatic system, other substituents than those defined for 40 R, R2 and R3, carrying the aromatic radical in the position or in front of the oxygen atom that joins the phosphorus atom with the aromatic system, a hydrogen atom, 45 X: 1 6 2, MOtfa? - «- * -» "- • '• y, z, p: independently, O, 1 or 2, being precise that x + y + z + p = 3. xoozA 1 /
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